Determination of Pb/(Zr plus Ti) and Zr/(Zr plus Ti) ratios of lead zirconate titanate surface by x-ray photoelectron spectroscopy

The quantitative analysis of the surface of lead zirconate titanate (PZT) ceramics, the compositions of which were in the ranges of 0.1 < Zr/(Zr + Ti) < 0.9 and 0.8 < Pb/(Zr + Ti) < 1.2, was conducted using X-ray photoelectron spectroscopy (XPS). The linear relationship between the corresponding XPS intensities and the atomic ratio Zr/(Zr + Ti) could be obtained as a calibration equation. Here, the newly derived proportionality factor was introduced for the cancellation of the systematic errors. The calibration equation for the atomic ratio Pb/(Zr + Ti) was also obtained in the same way. The 99.9% confidence intervals of the calibration equations for Zr/(Zr + Ti) and for Pb/(Zr + Ti) were all +/-2% and +/-3%, respectively, although they narrowed to +/-1% around the compositions of Zr/(Zr + Ti) = 0.5 and Pb/(Zr + Ti) = 1.0. This analytical method was successfully applied to the follow-up of the compositional change of the surface of the PZT ceramics through separate acid and heat treatments.